Polychlorinated Dibenzo-p-dioxins/furans Research Articles

Gas/particle partitioning of PCDD/Fs: Distributions and implications for available models

Polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) are semi-volatile organic compounds (SVOCs) existing in the atmosphere in the gas and particulate phase, remain persistent for a long time and pose a high risk to the environment and human health. In this study, PCDD/F measurements were made in an urban area between June 2022 and April 2023. In order to understand the fate of PCDD/Fs, the gas/particle (G/P) partitioning was studied. Although various models have been developed to determine the G/P partitioning of SVOCs, only logKp-logPL0, Junge-Pankow and Harner-Bidleman models are generally used for PCDD/Fs. In this study, nine different models (Junge-Pankow, Harner-Bidleman, Dachs-Eisenreich, Li-Ma-Yang, pp-LFER, mp-pp-LFER, QSPR, logKp-logPL0, logKp-logKOA) were employed to determine the G/P partitioning. To the best of our knowledge, pp-LFER, mp-pp-LFER and QSPR models were evaluated for PCDD/Fs for the first time in this study. In addition, the performance of the models within the equilibrium (EQ), non-equilibrium (NE) and maximum partitioning (MP) domain was investigated for PCDD/Fs for the first time in this study. Accordingly, models based on absorption in the EQ domain, adsorption in the NE domain and adsorption and absorption mechanisms in the MP domain were found to be effective in explaining the G/P transitions. It was determined that there is no equilibrium situation in the G/P partitioning. The Junge-Pankow, pp-LFER, Li-Ma-Yang and QSPR models under-predicted the particle fraction values while the other models showed a high prediction profile. The Li-Ma-Yang model showed the closest results to the measured particle fraction values, and it determined that deposition mechanisms are of non-negligible importance in the G/P partitioning of PCDD/Fs. One of the new models, the pp-LFER model, has shown remarkable success at high logKOA values. The mp-pp-LFER model, which overestimated the contribution of the adsorption mechanism, showed a very high prediction profile compared to the measured values.

Reuse potential of municipal solid waste incinerator bottom ash as secondary aggregate: Material characteristics, persistent organic pollutant content and effects of pH and selected environmental lixiviants on leaching behaviour

Increasing municipal solid waste (MSW) production poses challenges for sustainable urban development. Modern energy-from-waste (EfW) facilities incinerate MSW, reducing mass and recovering energy. In the UK, MSW incineration bottom ash (MSW IBA) is primarily reused in civil engineering applications. This study characterizes UK-produced MSW IBA, examining its pH-dependent leaching behaviour and response to environmental lixiviants. Results show predominant components include a melt phase, primary glass and fine ash aggregations, and a chemical composition dominated by SiO2 (30–50 %), CaO (∼15 %), Fe2O3 (∼10 %), and Al2O3 (∼8%). X-ray absorption near edge structure (XANES) analysis shows that Zn and Cu are most likely oxygen-bound (adsorbed to oxy-hydroxides and as oxides) with some sulphur bound. Polychlorinated biphenyls (PCBs) and polychlorinated dibenzodioxins/furans (PCDD/Fs) are well below regulatory limits, and polycyclic aromatic hydrocarbons (PAHs) were undetectable. Leaching tests indicate trace elements mobilize at pHs ≤ 6. With a natural pH of 11.3 and high buffering capacity, significant acid inputs to the MSW IBA are required to reach this pH, which are improbable in the environment. Wood chip additions increase leachate’s dissolved organic carbon (DOC) and reduce pH, but had minimal impact on metal-leaching behaviour. Synthetic plant exudate solutions minimally affect metal leaching at realistic concentrations, only enhancing leaching at ≥ 1500 mg l−1 DOC. This work supports MSW IBA’s low-risk in specified civil engineering applications.

Urban air PCDD/Fs: Atmospheric concentrations, temporal changes, gas/particle partitioning, possible sources and cancer risks

Polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) are pollutants of concern due to their toxic effects. No active sampling study on PCDD/Fs has been conducted in Bursa. This study aimed to fill this gap by measuring PCDD/F levels in the region. Accordingly, the samples were collected from an urban area in Bursa, covering four seasons between June 2022 and April 2023. The total (gas+particulate) ambient air concentrations were between 312.23 and 829.80 fg/m3 (mean: 555.05 ± 173.62 fg/m3). In terms of toxic equivalents (TEQ), the average concentration was 43.29 ± 9.18 fg WHOTEQ/m3. Based on the concentration values obtained, cancer and non-carcinogenic risk values of PCDD/Fs were calculated for three different age groups. The results indicated negligible health risks for all age groups. In addition, a seasonal assessment was also made and it was observed that PCDD/F concentration values varied with the ambient air temperatures. In general, higher values were measured in colder months compared to warmer months. This was probably due to the additional sources and adverse meteorological conditions. Moreover, the gas/particle partitioning of PCDD/Fs was investigated in detail. The average gas and particulate phase concentrations for PCDD/Fs were 101.81 ± 20.77 and 453.24 ± 172.50, respectively. It was found that an equilibrium state was not reached in the gas/particle partitioning. Two different gas/particle partition models based on adsorption and absorption mechanisms were compared, and the absorption model gave more consistent predictions. The Principal Component Analysis (PCA) was employed to identify the possible PCDD/F sources. The results indicated that the region was influenced by vehicle emissions, residential heating, organized industrial zones and metal recycling facilities. In addition, 72-hour backward air mass trajectory analyses were performed to understand the long-range transported air masses. However, it was found that the transported air masses did not significantly affect the concentration values measured in the sampling site.

Halogenated aromatic pollutants in routine animal-derived food of south China: Occurrence, sources, and dietary intake risks

Halogenated aromatic pollutants (HAPs) including polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), polychlorinated biphenyls (PCBs), polybrominated dibenzo-p-dioxins/furans (PBDD/Fs), and polybrominated diphenyl ethers (PBDEs) exhibit diverse toxicities and bio-accumulation in animals, thereby imposing risks on human via animal-derived food (ADF) consumption. Here we examined these HAPs in routine ADFs from South China and observed that PBDEs and PCBs showed statistically higher concentrations than PCDD/Fs and PBDD/Fs. PCDD/Fs and PCBs in these ADFs were mainly from the polluted feed and habitat of animals, except PCDD/Fs in egg, which additionally underwent selective biotransformation/progeny transfer after the maternal intake of PCDD/F-polluted stuff. PBDEs and PBDD/Fs were mostly derived from the extensive use of deca-BDE and their polluted environments. Significant interspecific differences were mainly observed for DL-PCBs and partly for PBDD/Fs and PBDEs, which might be caused by their distinct transferability/biodegradability in animals and the different living habit and habitat of animals. The dietary intake doses (DIDs) of these HAPs via ADF consumption were all highest for toddlers, then teenagers and adults. Milk, egg, and fish contributed most to the DIDs and risks for toddlers and teenagers, which results of several cities exceeded the recommended thresholds and illustrated noteworthy risks. Pork, fish, and egg were the top three risk contributors for adults, which carcinogenic and non-carcinogenic risks were both acceptable. Notably, PBDD/Fs showed the lowest concentrations but highest contributions to the total risks of these HAPs, thereby meriting continuous attention.

Evaluation of hexabromocyclododecane (HBCD), polybrominated dibenzo-p-dioxins/furans (PBDD/Fs) and polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) outflows during the destruction of HBCD wastes in a hazardous waste incinerator

This paper presents an evaluation of hexabromocyclododecane (HBCD), polybrominated dibenzo-p-dioxins/furans (PBDD/Fs) and polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) outflows during the destruction of HBCD waste stockpiles in IZAYDAS Hazardous Waste Incinerator (HWI) in Kocaeli, Türkiye. HBCD wastes containing 100 % pure HBCD were in 25 kg packages with 63 % Br content were co-incinerated in a 3-day test burn with average feed rate of 26 kg/h. HBCD, PBDD/Fs and PCDD/Fs were measured in the outlet streams to quantify the amount of unintended POPs releases associated with the processing of HBCD waste and to observe the POP removal performance of air pollution control equipment (APCE) of the incinerator. Total mass outflow rate of HBCDs is calculated as 2.6 g/day, corresponding to destruction efficiency of 99.9996 %. Total toxicity of the brominated dioxins was measured as 0.00044 ng TEQ/Nm3 on average, while highly brominated congeners are dominant. PCDD/F concentrations in the outflow streams during HBCD test burns are produced similar congener distributions with those given in the previous studies, with the dominance of 7,8-chlorinated congeners. Mass flows in the outlet streams indicated that the efficiency of ESP and wet scrubbers for the removal of PCDD/Fs and HBCDs. Flue gas concentrations of PCDD/Fs, HBCDs and PBDD/Fs obtained in HBCD burn test indicated that burning HBCD wastes cause no significant emissions as operational parameters and total halogen content in the menu are kept within the incinerator limits.

Short- and medium-chain chlorinated paraffins in breast milk in Shanghai, China: Occurrence, characteristics, and risk assessment

As novel contaminants, short-chain chlorinated paraffins (SCCPs) and medium-chain chlorinated paraffins (MCCPs) have been of great concern in the past several years. Shanghai was one of the provinces with the largest chlorinated paraffins (CPs) emission in China; nevertheless, there is currently little information on the human exposure to SCCPs and MCCPs, particularly MCCPs. In this study, 25 breast milk samples were collected in Shanghai from 2016 to 2017. The concentrations of SCCPs and MCCPs were determined using two-dimensional gas chromatography coupled with orbitrap high-resolution mass spectrometry (GC × GC-orbitrap-HRMS) to investigate their characteristics and assess the associated health risks for breast-fed infants. Compared with the previous studies in other areas, the current study presented the higher CPs concentrations, with median concentrations of SCCPs and MCCPs up to 771 and 125 ng/g lipid weight (lw), respectively. The exposure profiles of the CPs were characterized by C10 and Cl6-7 as the predominant congeners of SCCPs, while C14 and Cl7–9 were identified as the dominant groups of MCCPs. CP-42 and CP-52 were identified as potential sources of CPs found in breast milk samples collected in Shanghai. The concentrations of MCCPs exhibited a positive correlation (p value < 0.05) with the dietary consumption of meat and poultry. No significant positive correlations were observed for SCCPs and MCCPs with polychlorinated dibenzodioxins/furans (PCDD/Fs) congeners. A preliminary exposure assessment showed that SCCPs in breast milk potentially posed high risks to the breast-fed infants in Shanghai.

Health assessment of emerging persistent organic pollutants (POPs) in PM2.5 in northern and central Taiwan

Over the last two decades, Taiwan has effectively diminished atmospheric concentrations of polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) through the adept utilization of advanced technologies and the implementation of air pollution control devices. Despite this success, there exists a dearth of data regarding the levels of other PM2.5-bound organic pollutants and their associated health risks. To address this gap, our study comprehensively investigates the spatial and seasonal variations, potential sources, and health risks of PCDD/Fs, Polychlorinated biphenyls (PCBs), and Polychlorinated naphthalene (PCNs) in Northern and Central Taiwan. Sampling collections were conducted at three specific locations, including six municipal waste incinerators in Northern Taiwan, as well as a traffic and an industrial site in Central Taiwan. As a result, the highest mean values of PM2.5 (20.3–39.6 μg/m3) were observed at traffic sites, followed by industrial sites (14.4–39.3 μg/m3), and the vicinity of the municipal waste incinerator (12.4–29.4 μg/m3). Additionally, PCDD/Fs and PCBs exhibited discernible seasonal fluctuations, displaying higher concentrations in winter (7.53–11.9 and 0.09–0.12 fg I-TEQWHO/m3) and spring (7.02–13.7 and 0.11-0.16 fg I-TEQWHO/m3) compared to summer and autumn. Conversely, PCNs displayed no significant seasonal variations, with peak values observed in winter (0.05–0.10 fg I-TEQWHO/m3) and spring (0.03–0.08 fg I-TEQWHO/m3). Utilizing a Positive Matrix Factorization (PMF) model, sintering plants emerged as the predominant contributors to PCDD/Fs, constituting 77.9% of emissions. Woodchip boilers (68.3%) and municipal waste incinerators (21.0%) were identified as primary contributors to PCBs, while municipal waste incinerators (64.6%) along with a secondary copper and a copper sludge smelter (22.1%) were the principal sources of PCNs. Moreover, the study specified that individuals aged 19–70 in Northern Taiwan and those under the age of 12 years in Central Taiwan were found to have a significantly higher cancer risk, with values ranging from 9.26 x 10−9-1.12 x 10−7 and from 2.50 x 10−8-2.08 x 10−7respectively.

Distributions of PCDD/Fs, PCBs, and PCNs in coastal sediments collected from major industrial bays in South Korea

Polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polychlorinated naphthalenes (PCNs) were assessed in coastal sediments from industrial bays in South Korea to evaluate the pollution levels and their environmental impact. The mean sediment concentrations of Σ17 PCDD/Fs, Σ18 PCBs, and Σ15 PCNs were 198 ± 140, 3427 ± 7037, and 85 ± 336 pg/g dw, respectively. Generally, pollutant concentrations in the inner bay were higher than those in the outer bay, indicating the influence of industrial emissions and harbor activities. The primary sources were identified as steel manufacturing and wastewater treatment plants for PCDD/Fs, harbor and shipbuilding activities for PCBs, and combustion-related sources for PCNs. Notably, PCDD/F concentrations exceeded sediment guideline values. The combined effects of PCDD/Fs and PCBs demonstrated adverse impacts on aquatic organisms. Hence, the release of toxic pollutants into the marine environment could have potential biological effects due to the combined impact of these various compounds.

Polychlorinated Naphthalenes in Foods from the French Market: Occurrence, Dietary Exposure, and Evaluation of Relative Contributions to Dioxin-like Contaminants.

Despite the growing interest in PCNs and the dioxin-like toxicity exhibited by a number of congeners, a comprehensive assessment of their contribution to the cocktail of dioxin-like contaminants is still lacking. To address such a shortcoming, this study investigated the PCN contamination in foodstuffs recently acquired in France, together with that of the regulatory polychlorinated dibenzodioxins/furans (PCDD/Fs) and polychlorinated biphenyls (PCBs). PCNs were ubiquitous at levels (∑70 PCNs = 2.5-150 pg g-1 wet weight) similar to those reported in other countries, with maximum concentrations observed in fish and fishery products from the North-East Atlantic Ocean. Their congener patterns further suggested unintentional releases of PCNs, while those of the other foodstuffs were correlated to the historical PCN profiles. Low risk from dietary exposure was estimated (∑70 PCNs-EDIs of 60-360 pg kg-1 bw d-1, ∑24 PCNs-TEQ-EDIs of 8 × 10-3-2.2 × 10-2 pg TEQ kg-1 bw d-1), with milk and dairy products being the highest contributors, followed by meat and meat products. Finally, the rather high contributions of PCNs to the total PCNs+PCDD/Fs+PCBs concentrations (0.9-50%, average of 9%) and the toxic equivalents (0.2-24%, average of 5%) show that these substances are not minor components of the PCNs+PCDD/Fs+PCBs cocktail.

Serum PCDD/F levels in metropolitan populations living near a municipal solid waste incinerator in Eastern China

Ambient exposure to polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) is suspected to cause adverse human health outcomes. Herein, serum samples from 40 residents in the neighborhood of a municipal solid waste incinerator (MSWI) in the metropolitan area were measured for PCDD/Fs. The mean toxic equivalent (TEQ) concentration of total PCDD/Fs in human serum samples was 16.8 pg TEQ/g lipid. Serum PCDD/F levels were significantly higher in residents adjacent to the MSWI than in those from areas far from the emission source (p < 0.01). In addition, there were no significant associations between serum PCDD/Fs levels and factors, such as gender, age, and BMI in donors. For non-occupationally exposed populations, OCDD and 1,2,3,7,8-PeCDD in serum are available as indicators of total PCDD/Fs and total TEQ, respectively. The atmospheric PCDD/Fs levels were within a relatively low range in areas upwind and downwind of the MSWI. The results of the principal component analysis showed a distinct difference in PCDD/F congener patterns between air and serum samples, suggesting inhalation exposure could have a limited influence on the human body burden. Our findings will deepen the current knowledge of endogenous PCDD/F exposure in urban populations, and also facilitate public health protection strategies near MSWIs.

Spatial distribution, source identification, and risk assessment of polychlorinated organic pollutants (PCDD/Fs and DL-PCBs) in the sediments of the largest urban water supply area (Iznik lake) in the Marmara region, Bursa, Türkiye

Iznik lake is the biggest lake in the Marmara region, which is the most industrialized and populated area of Türkiye. The lake is one of Türkiye's most important water supply areas and is located nearby the Iznik district of Bursa, with a population of about 45,000. It is being used for irrigation and fishery production, but not for drinking water. In this paper, the distribution, pollution source, and risk assessment of polychlorinated dibenzodioxins/furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in the surface sediments of Iznik lake and streams (both flowing to and flowing from the lake) were investigated. Six surface sediments collected from the lake and four surface sediments collected from the streams were analyzed in high-resolution gas chromatography-mass spectrometry (HR/GC–MS) system in accordance with EPA 1613 and EPA 1668 methods. The concentration ranges of the ∑PCDD/Fs is 21.4 pg/g d.w. (inside the lake (IZ-6)) – 54.5 pg/g d.w. (Gülayağı stream (IZ-8)) and ∑DL-PCBs is 13.5 pg/g d.w. (inside the lake (IZ-3)) – 46.3 pg/g d.w. (Olukdere (IZ-7)) respectively, with 2.68 pg TEQ/g d.w. on average. The results showed that the high chlorinated (Hepta – Octa CDD/Fs) dioxins/furans and pentachlorinated PCBs (PCB 118 and 105) are dominant in the sediments. A detailed assessment of PCDD/F congener profiles observed in the lake sediments speculated that the wastewater discharges to the lake could be the main pollution source, while other sources such as open burning activities, runoff of pesticide residues from agricultural areas and atmospheric deposition may have some contribution also. The health risk assessment performed for polluted sediment demonstrated that, in the worst case, dioxin-like (PCDD/Fs and DL-PCBs) concentration was a total intake of 0.37 pg TEQ/kg body weight/day, no exceeds the tolerable daily intake amount, where fish consumption accounts for nearly all of the total intake.

Occurrence and carcinogenic potential of airborne PBDD/Fs and PCDD/Fs around a large-scale municipal solid waste incinerator: A long-term passive air sampling study

Municipal solid waste incinerator (MSWI) not only is deemed one of the uppermost sources of polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), but also produces substantial amount of polybrominated dibenzo-p-dioxins/furans (PBDD/Fs) owing to the existence of brominated flame retardants (BFRs) in the waste. So far, however, PBDD/Fs in the vicinal environments of MSWI and their associated risks remain rarely studied. Based on a one-year passive air sampling (PAS) scheme, we investigated airborne PBDD/Fs and PCDD/Fs around a large-scale MSWI that has been operated for multi-years. Both the concentrations of PBDD/Fs and PCDD/Fs showed spatially decreasing trends with the distance away from the MSWI, confirming the influence of the MSWI on the dioxin levels in its ambient air. But its influence on PBDD/Fs was less because PBDD/Fs exhibit lower volatility and therefore lower gaseous concentrations than PCDD/Fs. Compared to the existing global data of airborne PCDD/Fs and PBDD/Fs, our data of the MSWI vicinity were at medium levels, despite PAS samples only represent the concentrations of gaseous dioxins in theory. The seasonal data suggest that meteorological conditions exerted apparent influences over the concentrations and sources of airborne dioxins around the MSWI. As for PCDD/Fs, the MSWI was diagnosed as their uppermost source, followed by local traffic and volatilization/deposition. Whereas the top three PBDD/F sources were related to PBDEs, bromophenol/bromobenzene, and traffic vehicles, respectively. The bioassay-derived TEQs based on the aryl hydrocarbon receptor activation of airborne dioxins around the MSWI were one or two orders of magnitudes higher than their concentration-based TEQs, and the corresponding carcinogenic risks at some MSWI-vicinal sites exceeded the acceptable threshold proposed by the U. S. EPA (10−6 ∼ 10−4) and deserve continuous attention.

PCDD/F adsorption enhancement over nitrogen-doped biochar: A DFT-D study

Polychlorinated dibenzo-p-dioxin/furans (PCDD/F) have a great threat to the environment and human health, resulting in controlling PCDD/F emissions to regulation far important for emission source. Considering 2,3,4,7,8-pentachlorodibenzo-p-furan (PeCDF) identified as the most contributor to international toxic equivalent, 2,3,4,7,8-PeCDF can be considered as the target molecule for the adsorption of PCDD/F emission from industries. With the aim to in-depth elucidate how different types of nitrogen (N) species enhance 2,3,4,7,8-PeCDF on the biochar and guide the specific carbon materials design for industries, systematic computational investigations by density functional theory calculations were conducted. The results indicate pristine biochar intrinsically interacts with 2,3,4,7,8-PeCDF by π-π electron donor and acceptor (EDA) interaction, six-membered carbon rings of PeCDF parallel to the biochar surface as the strongest adsorption configuration. Moreover, by comparison of adsorption energy (−150.16 kJ mol−1) and interaction distance (3.593 Å) of pristine biochar, environment friendly N doping can enhance the adsorption of 2,3,4,7,8-PeCDF on biochar. Compared with graphitic N doping and pyridinic N doping, pyrrolic N doping biochar presents the strongest interaction toward 2,3,4,7,8-PeCDF molecule due to the highest adsorption energy (−155.56 kJ mol−1) and shortest interaction distance (3.532 Å). Specially, the enhancing adsorption of PeCDF over N doped biochar attributes to the enhancing π-π electron EDA interaction and electrostatic interaction. In addition, the effect of N doping species on PeCDF adsorbed on the biochar is more than that of N doping content. Specially, the adsorption capacity of N doping biochar for PCDD/F can be improved by adding pyrrolic N group most efficiently. Furthermore, pyrrolic N and pyridinic N doping result in the entropy increase, and electrons transform from pyrrolic N and pyridinic N doped biochar to 2,3,4,7,8-PeCDF molecule. A complete understanding of the research would supply crucial information for applying N-doped biochar to effectively remove PCDD/F for industries.

Development of a field-deployable analytical workflow for determining current status and indicative human health risks at a historic dl-POPs hotspot

This paper introduces an integrated workflow that effectively evaluates environmental and health risks of dioxin-like Persistent Organic Pollutants (dl-POPs) at industrial hotspot regions. The developments of validated, cost effective and user-friendly analytical strategies which can be field deployable are quintessential for routine monitoring of dl-POPs, particularly in developing countries. This study addresses the lacunae by enabling an exclusive gas chromatography triple quadrupole mass spectrometer based analytical workflow substituting conventional magnetic sector high resolution mass spectrometer technique and validated the methodology as per the European Union regulation 644/2017. The viable monitoring utility of the methodology for predicting enviro-food-health nexus was field-tested by analyzing fish and sediment samples from the Eloor-Edayar industrial belt, a solitary POPs hotspot in India. The profiles of congeners indicate that dl-POPs were formed through precursor pathways, suggesting the potential release of chlorinated precursor species from surrounding industrial area as the root cause. Fish samples from hotspots were observed to have 8 times higher levels of polychlorinated dibenzo-p-dioxin/furans (PCDD/Fs) and 30 times higher levels of polychlorinated biphenyls (PCBs) than the control sites. A strong statistically significant (p < 0.05) positive correlation was observed between dl-POPs levels in fish and sediment samples at the study site and the Biota sediment accumulation factors for PCDD/Fs and dl-PCBs ranged from 0.019 to 0.092 and 0.004 to 0.671 respectively. The estimated weekly intake from fish consumption in the study region was observed to be 3 to 24 times higher than the maximum levels set by the European food safety authority (2 pgTEQ kg−1bwweek−1). Hence, the periodic surveillance of dl-POPs employing user friendly/validated confirmatory tools stands highly imperative to safeguard human health and environment. Keywords: Dioxin and PCBs, GC-MS/MS, POPs Hotspot, Biota-sediment accumulation factor, Correlation analysis, Health risk assessment.

Levels, enrichment characteristics and dietary intake risk of polychlorinated dibenzo-p-dioxin/furans in traditional smoked pork

The concentrations and TEQs of polychlorinated dibenzo-p-dioxin/furans (PCDD/Fs) in traditional smoked pork were significantly higher than those in raw pork, and mainly distributed in the surface layer. The main enriched congeners during traditional smoking were 2378-TCDF, 12378-PeCDF, 23478-PeCDF, 1234678-HpCDF, OCDF, 1234678-HpCDD and OCDD. The ability of each congener to transfer from the surface to the inner part was various. According to the dietary habits of local residents, PCDD/Fs in more than half of the traditional smoked pork samples posed a potential carcinogenic risk, and the risk in the surface samples were 1.02–10.2 times that of the corresponding inner samples. Some variables might be the important factors affecting the concentration of PCDD/Fs in smoked pork, such as the duration of smoking and the kind of fuel. It is recommended to achieve lower risk by reducing the consumption of smoked pork, especially the surface layer of smoked pork, and innovating traditional smoking technologies.

Occurrence and congener profiles of dioxins (PCDDs), furans (PCDFs) and polychlorinated biphenyls (PCBs) in ovine and caprine milk samples collected in a very polluted site in Central Italy

Concentrations of 7 polychlorinated dibenzo-p-dioxins (PCDDs), 10 polychlorinated dibenzofurans (PCDFs) and 18 polychlorinated biphenyls (PCBs), including 12 dioxin-like (DL-PCBs) and 6 non-dioxin-like PCBs (NDL-PCBs) were measured in 16 ovine and caprine milk samples collected in the territory of Bussi sul Tirino, central Italy, a Site of National Interest (SNI) due to its high and widespread environmental pollution. All the analyzed samples were compliant with the maximum levels fixed by Commission Regulation (EU) 1259/2011 for the content of PCDD/Fs and the sum of PCDD/Fs and DL-PCBs. In two cases, contamination levels of the sum of PCDD/Fs and DL-PCBs were higher than the action levels fixed by EU Recommendation 663/2014. The statistical analysis, performed by Principal Component Analysis (PCA), revealed that the differences in contamination profiles of the different milk samples were independent of the distance of the farms from the Bussi illegal landfill but likely related to local emission sources influencing the exposure to POPs of studied animals.

Use of different endpoints to determine the bioavailability of polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) and polychlorinated biphenyls (PCBs) in Sprague–Dawley rats

Liver, fat (adipose tissue), blood, and feces are common endpoints used to determine the bioavailability of persistent organic pollutants (POPs). However, it is not known whether the bioavailability of each endpoints is comparable or whether there is a comprehensive endpoint that can be used for all congeners for the measurement of bioavailability. In this study, we observed the accumulation and distribution of 10 polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) and 18 polychlorinated biphenyls (PCBs) in different organs of Sprague–Dawley (SD) rats and calculated the bioavailability based on feces, liver, and fat endpoints. Our results indicated that PCB 126, PCB 169, and 50% of PCDD/F congeners were mainly accumulated in the liver, with a bioavailability ranging from 28.9 to 50.6%. On the other hand, higher chlorinated (> 5 Cl) PCB congeners were mainly accumulated in adipose tissues, with a bioavailability ranging from 20.1 to 82.2%, while lower chlorinated (< 5 Cl) pollutants, such as 2,3,7,8-TeCDF, 2,3,7,8-TeCDD, 1,2,3,7,8-PeCDF, and PCB 28, 52, 77, 81, were likely metabolized over 36% in rats during the 8-week experimental period. If we considered metabolization (degradation) as a type of bioavailable process, then the fecal endpoint was a feasible option. However, if we considered the selective accumulation behavior of some congeners in different organs/tissues, then there was no single comprehensive endpoint suitable for all congeners. Lastly, female rats showed significantly higher PCDD bioavailability than male rats at low dose level (0.2 ng/100 g b.w./d); however, the difference in PCB bioavailability between female and male rats was not significant.

Polybrominated dibenzo-p-dioxins/furans and their chlorinated analogues in sediments from a historical hotspot for both brominated flame retardants and organochlorine pesticides

Polybrominated dibenzo-p-dioxin/furans (PBDD/Fs) and polychlorinated dibenzo-p-dioxin/furans (PCDD/Fs) in the environment are closely related to their precursors, brominated flame retardants (BFRs) and organochlorine pesticides (OCPs). However, their change trends following the regulation of BFRs and OCPs remain incompletely characterized. Here, we examined PBDD/Fs and PCDD/Fs in sediments from a historical hotspot for both BFRs and OCPs, namely the Pearl River Delta (PRD), China. PBDD/Fs showed ubiquity in these samples but significantly lower concentrations than PCDD/Fs. Spatially, the occurrence of PBDD/Fs was positively correlated with local development levels and sediments from highly urbanized/industrialized areas showed higher and increasing PBDD/F concentrations. Polybrominated diphenyl ether (PBDE)-related products/industries were the greatest PBDD/F contributors to the PRD, followed by bromo-phenol/benzene-related products/industries. PCDD/Fs in PRD sediments showed significant positive correlations with local grain planting area, yield, and pesticide consumption. The historical use of pentachlorophenol (PCP)/PCP-Na and biomass open-burning were the leading PCDD/F sources of the PRD agricultural/rural areas, where the concentrations and toxic equivalent quantities (TEQs) of PCDD/Fs in sediments changed very little over the past decade. Anthropogenic thermal processes involved in metallurgy, waste incineration, and vehicles were the greatest PCDD/F contributors in the PRD urban/industrial areas, where the PCDD/F concentrations in sediments almost doubled over the last decade. This finding indicates the increasing PCDD/F contributions of industrial and municipal activities in the PRD, despite the implementation of strict emission standards. Over sixty percent of the samples showed TEQs that surpassed the low-risk threshold specified for mammalian life by the U.S. EPA (2.5 pg TEQ g−1) and warrant continuous attention.

Health risk assessment to polychlorinated naphthalenes dioxin-like compounds in French sea food consumers

There has been a recent revival of interest in some historical contaminants such as polychlorinated naphthalenes (PCNs). However, occurrence data are still lacking in some countries although industrial production of PCNs has been reported. This observation led to the first ever assessment of their presence in fish and seafood products in France in the present work. Their analysis was integrated in an already validated method applied for polychlorinated dibenzodioxins/furans (PCDD/Fs) and polychlorinated biphenyls (PCBs), based on the structural similarity existing between these POPs.Performances of the method (LODs in the range 0.10–0.28 pg g−1 wet weight (ww), LOQs in the range 0.33–0.93 pg g−1 ww), enabled monitoring 69 di-to octachlorinated congeners in a large representative set of fish and seafood samples collected in 2005 in four coastal areas of the French mainland (n > 30). Their systematic presence was demonstrated in all the investigated seafood products, with levels (ΣPCNs in the range 2–440 pg g−1 wet weight) close to those already reported in other European fish and seafood sampled at a similar period. In addition, the robust measurement of almost all possible PCNs (69/75) allowed a fine interpretation of the observed profiles, highlighting in particular the specificities between species and fishing areas. Compared to the PCDD/Fs, PCBs, and polybrominated diphenylethers levels also measured for this set of samples, PCNs were observed as minor contributors to total concentrations (0.05–3.2%). The specific PCN related dietary dioxin-like exposure could be evaluated at 0.028–0.051 pg of toxic equivalent (TEQ) per kg of body weight per week for an adult, based on fish and seafood consumption only. Overall, this study provides the first baseline data on the occurrence of a large number of PCNs in France, which will allow future evaluation of temporal trends and associated risks.

Characterization of Dioxins and Heavy Metals in Chelated Fly Ash

Municipal solid waste incineration (MSWI) fly ash contains highly toxic heavy metals and polychlorinated dibenzo dioxins/furans (PCDD/Fs), which are a type of hazardous waste. The pollution characteristics of fly ash have changed with the development of stoker grate incinerators and the fly ash treatment technology; however, no research has been focused on this in recent years. In this study, 12 fly ash samples were collected from 9 grate power plants in southeastern China, and their PCDD/Fs and heavy metal concentrations were determined and compared to previous fly ash data. The PCDD/Fs concentration in fly ash was in the range of 0.002–0.051 ngI-TEQ/g, with an average of 0.027 ngI-TEQ/g. Furthermore, 1,2,3,4,6,7,8-HpCDD and OCDD made the most significant contributions to PCDDs. The distribution of 10 dioxins exhibited bimodal, unimodal, and normal characteristics. Linear fitting demonstrated a strong correlation between toxicity and 1,2,3,7,8-PentaCDD, 1,2,3,7,8-PentaCDF, and 2,3,4,7,8-PentaCDF. Concerning heavy metals, Pb poses a significant environmental risk. This is the first time that fly ash treated with a chelating agent has been thoroughly analyzed, which is vital for understanding the pollution level and treatment of fly ash derived from current power plants.